US5550209A - Monodispersed polymer or copolymer and a preparation process thereof - Google Patents

Monodispersed polymer or copolymer and a preparation process thereof Download PDF

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US5550209A
US5550209A US08/395,889 US39588995A US5550209A US 5550209 A US5550209 A US 5550209A US 39588995 A US39588995 A US 39588995A US 5550209 A US5550209 A US 5550209A
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polymer
monodispersed
group
lactone
carbonate
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Shohei Inoue
Takuzo Aida
Masaki Akatsuka
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Daicel Corp
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Daicel Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides

Definitions

  • the present invention relates to a lactone polymer, a carbonate polymer and a lactone-carbonate block copolymer, and a lactone-carbonate random which are mono-dispersed, that is, which have a molecular weight distribution of nearly 1, or in which the purity of a polymer component having a unitary structure is very high. Furthermore, the present invention relates to a process for the preparation thereof.
  • the present invention relates to mono-dispersed polymers or copolymers which can be preferably employed in uses such as starting materials for polyurethanes or coatings, and a modifier for resins in which there are required high added-values and advanced performance, and relates to the process for the preparation thereof.
  • Ring-opening polymerization of lactones or cyclic carbonates is broadly divided into two categories of polymeri-zation.
  • the former is anionic polymerization in which organo-metallic compounds are generally employed as an initiator.
  • the latter is polymerization in which there are employed compounds having at least one active hydrogens such as water and alcohols which are initiators in the presence of various Lewis acids in a broad sense, which are catalysts.
  • n-butyl lithium, tert-butoxy potassium, sodium methoxide, and rare earth metal complexes as the organometallic compounds which are initiators.
  • Kokai No. 37737/1971 discloses a polystyrene-polycarbonate block copolymer and the like
  • Kokai No. 294326/1990 discloses a polycaprolactone-polyneopentylglycol carbonate block copolymer and the like
  • Kokai No. 500982/1993 disclose processes for the preparation of polycaprolactones in which rare earth metal complexes are employed.
  • Lewis acids in a broad sense such as sulfuric acid, p-toluene sulfonic acid, quaternary ammonium salts, boron trifluorides, stannous tetrachloride, trialkyl aluminum, tetrabutyl titanate, and dibutyl tin oxide, and the like.
  • Lewis acids have a function capable of accelerating nucleophilic property in initiators such as water and alcohols together with lowering the energy required in the ring-opening reaction of lactone monomers or cyclic carbonate monomers.
  • Japanese Patent Examined publication (Kokoku) No. 56251/1991 discloses that polymers having a molecular weight distribution ranging from 1.54 to 1.76 which are measured with a GPC method in the presence of ethylene glycol as an initiator and halogenated stannous compounds in comparison with polymers prepared using conventional tetrabutyl titanate as a catalyst.
  • EP-A-0600417 discloses a process for the preparation of hydroxy-terminated linear carbonates having molecular weight distribution ranging from 1.7 to 2.1 by the reaction of polyvalent alcohols or hydroxy alkyl(meth)acrylates with cyclic carbonates in the presence of a catalyst selected from a Bronsted acid, an onium salt thereof, a strongly acidic ion exchange resin, an alkyl alkali metal, an alkali metal alkoxide, an amine, a tin compound, a tungsten compound, a titanium compound, and a zinc compound.
  • a catalyst selected from a Bronsted acid, an onium salt thereof, a strongly acidic ion exchange resin, an alkyl alkali metal, an alkali metal alkoxide, an amine, a tin compound, a tungsten compound, a titanium compound, and a zinc compound.
  • a first aspect of the present invention relates to a process for the preparation of any one of a monodispersed lactone polymer, a monodispersed carbonate polymer, and a monodispersed lactone-carbonate copolymer which comprises the ring-opening addition reaction of a lactone monomer and/or a cyclic carbonate monomer with a ring-opening initiator in the presence of an organic aluminum-based Lewis acid represented by general formula (I), ##STR2## wherein R is an alkyl group having a carbon number ranging from 1 to 4, Y is independently selected from a substituted group, and p is any one of 1, 2, and 3.
  • a second aspect of the present invention relates to a monodispersed (co)polymer having a plurality of hydroxyl groups represented by general formula (III), ##STR3## wherein R 1 is ##STR4## k is an interger ranging from 4 to 8, R 2 is an alkylene group having a carbon number ranging from 1 to 10, n1 and n2 are an integer ranging from 0 to 100 which are not simultaneously 0, n3 is an integer ranging from 1 to 10, m is an integer ranging from 2 to 10, and z is a residual group of a polyvalent alcohol having functionality of m.
  • a third aspect of the present invention relates to a (meth)acrylic-modified monodispersed lactone and/or carbonate (co)polymer having one hydroxyl group represented by general formula (IV), ##STR5## wherein R 3 is a hydrogen or methyl, R a and R b are independent hydrogen or a methyl group, k is an integer ranging from 4 to 8, R 1 and R 2 are an alkylene group having a carbon number ranging from 1 to 10, n1 and n2 are an integer ranging from 0 to 100 which are not simultaneously 0, and n3 is an integer ranging from 1 to 10.
  • FIG. 1 is a 1 H-NMR spectra chart related to the carbonate polymer obtained in Example 1.
  • FIG. 2 is a 1 H-NMR spectra chart related to the lactone polymer obtained in Example 2.
  • FIG. 3 is GPC charts related to the neopentyl glycol carbonate polymer and block copolymer obtained in Example 3.
  • FIG. 4 is a 1 H-NMR spectra chart related to the block copolymer obtained in Example 3.
  • FIG. 5 is a GPC chart related to the block copolymer obtained in Example 10.
  • FIG. 6 is a GPC chart related to the lactone polymer in halfway sampling and a GPC chart related to the block copolymer obtained in Example 11.
  • a process for the preparation of any one of a monodispersed lactone polymer, a monodispersed carbonate polymer, and a monodispersed lactone-carbonate copolymer which comprises a ring-opening addition reaction of a lactone monomer and/or a cyclic carbonate monomer with a ring-opening initiator in the presence of an organic aluminum-based Lewis acid represented by general formula (I), ##STR6## wherein R is an alkyl group having a carbon number ranging from 1 to 4, Y is independently selected from a substituted group, and p is any one of 1, 2, and 3.
  • the content of a (co)polymer component having a unitary structure is not less than 50% preferably 70%, and more preferably 90% based on the total components by a measurement with gel permeation chromatography (hereinafter, referred to as GPC).
  • the number average molecular weight of a polymer or copolymer is not less than 1000, it is a unimodal polymer or copolymer and it has a value of a weight average molecular weight/number average molecular weight (hereinafter, referred to as the molecular weight distribution) ranging from 1.0 to 1.5, preferably 1.0 to 1.2, and more preferably 1.0 to 1.1 as determined by measurement using GPC.
  • the molecular weight distribution ranging from 1.0 to 1.5, preferably 1.0 to 1.2, and more preferably 1.0 to 1.1 as determined by measurement using GPC.
  • Initiators in the present invention include a compound having at least one active hydrogen atoms such as a hydroxyl group, amino group, carboxylic group, thiol group, and an active methylene group put between at least two electron-attractive groups in the molecule.
  • aliphatic alcohols and aliphatic polyvalent alcohols. More specifically, there are exemplified methanol, ethanol, isopropanol, ethyleneglycol, diethylene-glycol, butanediol, hexamethyleneglycol, neopentyl glycol, trimethylolpropane, pentaerythritol, 2-hydroxyethyl(meth)-acrylate, 4-hydroxybutyl(meth)acrylate, allylalcohol, a polyvinylalcohol, a 2-hydroxyethyl(meth)acrylate-modified polymer, and an adduct of ethylene oxide to bisphenol A, and the like.
  • lactone monomers in the present invention there can be generally employed publicly known lactones and, specifitally, delta-varelo-lactone, epsilon-caprolactone, and an alkylated lactone thereof are preferably employed from a general or practical point of view.
  • epsilon-caprolactone is preferably employed because it is manufactured industrially.
  • One or more of the lactone monomers may be employed.
  • cyclic carbonate monomers there can be preferably employed propylglycol carbonate, 2-methylpropylglycol carbonate, neopentyl glycol carbonate, and the like.
  • One or more of the cyclic carbonate monomers may be employed.
  • lactone monomers and cyclic carbonate monomers may be also employed as an admixture to prepare a copolymer.
  • the lactone monomers, the cyclic carbonate monomers, and the admixture thereof are employed in a molar ratio ranging from 1 to 10,000, preferably from 1 to 5,000, and more preferably from 1 to 1,000 based on 1 mol of initiators.
  • the organic aluminum-based Lewis acid in the present invention is represented by above-described general formula (I).
  • R is an alkyl group having a carbon number ranging from 1 to 4
  • Y is independently selected from a substituted group
  • p is any one of 1, 2, and 3.
  • the alkyl group R specifically includes the methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, and tert-butyl group.
  • Specific examples of the substituted group Y independently include hydrogen, an alkyl group such as a methyl group, ethyl group, butyl group, and tert-butyl group, and the like, an aryl group such as the phenyl group, and the like, a halogen such as fluorine, chlorine, and iodine, and the like, a trimethylsilyl group, and a trimethylgelmil group, and the like.
  • P is any one of 1, 2, and 3.
  • p is 1, although the ring-opening addition reaction rate of the cyclic monomers becomes large, there is exhibited a tendency in broadening of the molecular weight distribution of the polymer or copolymer and further, in the case when p is 3, it is difficult to prepare catalysts, resulting in that p is most preferably 2.
  • the organic aluminum-based Lewis acid in the present invention represented by above-described general formula (I) can be prepared by a reaction of an alkylphenol such as 2,6-diphenylphenol, 2,6-ditert-butyl-4-methylphenol, and 2,4,6-trichlorophenol, 2,4,6-tritert-butylphenol, etc. with a trialkylaluminum such as tri-methylaluminum and triisobutyl-aluminum, etc.
  • an alkylphenol such as 2,6-diphenylphenol, 2,6-ditert-butyl-4-methylphenol, and 2,4,6-trichlorophenol, 2,4,6-tritert-butylphenol, etc.
  • a trialkylaluminum such as tri-methylaluminum and triisobutyl-aluminum, etc.
  • an excessive amount of alkylphenol is allowed to react with the trialkylaluminum, specifically, in a molar ratio ranging from 5/1 to 1/1, preferably from 2.5/1 to 2/1.
  • the reaction is preferably carried out in a temperature ranging from 0° C. to room temperatures.
  • the organic aluminum-based Lewis acid is obtained in the state of a white-colored crystalline after washing with an inert solvent such as hexane or in the state of a solution thereof.
  • an organic aluminum-based Lewis acid represented by general formula (II) as described below is preferably employed. ##STR7##
  • R is an alkyl group having a carbon number ranging from 1 to 4, X is independently selected from the tert-butyl group, phenyl group, chlorine, bromine, and iodine. Y is independently any substituted group.
  • the catalysts are not sterically hindered so much by each other and, as a result, associability appears and the coordinating effect is decreased by the lactone monomer, the cyclic carbonate monomer, and the admixture thereof to the catalysts, resulting in a condition under which a highly monodispersed polymer or copolymer can be preferably prepared.
  • the organic aluminum-based Lewis acid represented by general formula (I) is employed in a molar ratio ranging from 0.0001 to 1, preferably from 0.001 to 0.5, more preferably from 0.05 to 0.2 based on 1 mol of the initiators.
  • the molar ratio is less than 0.0001, the ring-opening reaction of the cyclic monomers is slow, and in the case when it exceeds 1, it is meaninglessly only excessive in a practical manner.
  • improved apparatuses for the preparation are preferably employed so that the mixing of moisture and other impurities into starting materials can be prevented.
  • the total amount of the above-described impurities including moisture is desirably controlled within an amount of less than 5,000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm based on the total amount of starting materials.
  • solvents may also be employed.
  • solvents there are exemplified aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and the like, aromatic hydrocarbons such as benzene, toluene, xylene, and the like, and halogenated hydrocarbons such as chloroform, dichloromethane, and the like which do not have an active hydrogen atom such as hydroxyl group.
  • aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and the like
  • aromatic hydrocarbons such as benzene, toluene, xylene, and the like
  • halogenated hydrocarbons such as chloroform, dichloromethane, and the like which do not have an active hydrogen atom such as hydroxyl group.
  • the solvents may be preferably employed in an appropriate amount without any limitations.
  • the initiators, lactone monomers, and/or cyclic carbonate monomers which are the starting materials in the present invention, catalysts, and optional solvents may be fed into a reaction vessel in any order without any limitations for methods to be fed.
  • a random copolymer can be prepared, and, when either monomer is firstly charged for carrying out a polymerization, and then another monomer is secondly charged after polymerization was completed, a block copolymer can be prepared.
  • a reaction may be carried out at temperatures ranging from 0° to 200° C., and preferably from room temperatures to 180° C. or so. Even in the case when the reaction is carried out at more than 180° C., although the molecular weight distribution in polymers or copolymers obtained does not broaden so much, the reaction rate is unpreferably lowered at temperatures higher than the initiation of decomposition of the organic aluminum-based Lewis acid.
  • the reaction is not particularly limited by other conditions except the above-described conditions.
  • an organic aluminum-based Lewis acid which is a catalyst may also be optionally separated from polymers or copolymers produced after the completion of the ring-opening addition reaction.
  • solvent separation there are exemplified solvent separation, absorption, distillation or evaporation at reduced pressures, and filtration, and the like.
  • solvent separation process there can be carried out all of the methods in which the difference in solubility between polymers or copolymers produced and the organic aluminum-based Lewis acid is applied.
  • absorption process there can be carried out chromatography in which there are employed substrates such as activated carbon, silica gel, alumina, graphite, a polymer having hydroxyl group, amino group, carboxylic group, and sulfoxide group, and the like, and a porous ceramic, and, further, an electrophoresis method. Distillation or evaporation at reduced pressures is an appropriate separation process in the case of a resulting lactone polymer having a low molecular weight.
  • a membrane process can be applied using the difference in molecular sizes.
  • a monodispersed polymer or copolymer having a plurality of hydroxyl groups represented by general formula (III), ##STR8## wherein R 1 is ##STR9## k is an integer ranging from 4 to 8, R a and R b are an independent hydrogen or methyl group, and R 2 are an alkylene group having a carbon number ranging from 1 to 10, n1 and n2 are an integer ranging from 0 to 100 which are not simultaneously 0, n3 is an integer ranging from 1 to 10, m is an integer ranging from 2 to 10, and Z is a residual group of a polyvalent alcohol having the functionality of m.
  • general formula (III) ##STR8## wherein R 1 is ##STR9## k is an integer ranging from 4 to 8, R a and R b are an independent hydrogen or methyl group, and R 2 are an alkylene group having a carbon number ranging from 1 to 10, n1 and n2 are an integer ranging from 0 to 100 which are not simultaneously 0, n3 is an integer
  • the polymer or copolymer having a plurality of hydroxyl groups represented by general formula (III) of the present invention has at least two hydroxyl groups at terminals in the molecule, which is characterized by being monodispersed, and which includes a lactone polymer, a carbonate polymer, and a lactone-carbonate block or random copolymer.
  • the present invention relates to the lactone polymers having molecular weight distribution ranging from 1.0 to 1.5, and not containing cyclic dimers, that is, which have a high purity, and relates to the various monodispersed polycarbonate polymers, lactone-polycarbonate random, or block copolymers.
  • R 1 that is R a , R b and k depend upon the lactone compound to be employed, for example, in the case when ⁇ -caprolactone is employed, R a and R b are hydrogen, and k is 5.
  • R Z is any one of a trimethylene group, 2-methyltrimethylene group, 2,2-dimethyltrimethylene group, and tetramethylene group which depends upon a cyclic carbonate monomer to be employed, for example, in the case when neopentylglycol carbonate is employed, R 2 is --CH 2 C(CH 3 ) 2 CH 2 --.
  • n1 and n2 are an integer ranging from 0 to 100, preferably ranging from 5 to 50 which are not simultaneously 0, n3 is an integer ranging from 1 to 10, preferably ranging from 1 to 5, and m is 2, 3, or 4.
  • Z is a residual group of a polyvalent alcohol which includes ethylene glycol, diethyleneglycol, butanediol, hexamethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, a polyvinylalcohol, a 2-hydroxyethyl-(meth)acrylate polymer, a 2-hydroxybutyl(meth)acrylate polymer, and an adduct of ethylene oxide to bisphenol A, and the like.
  • a polyvalent alcohol which includes ethylene glycol, diethyleneglycol, butanediol, hexamethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, a polyvinylalcohol, a 2-hydroxyethyl-(meth)acrylate polymer, a 2-hydroxybutyl(meth)acrylate polymer, and an adduct of ethylene oxide to bisphenol A, and the like
  • the molecular design is easy because of the narrow molecular weight distribution and a minor amount of impurities, resulting in the capability of preparing polyurethanes having improved properties and outer appearance, and improving workability in manufacturing.
  • polyurethanes having a higher molecular weight can be designed; (2) polyurethanes having an improved modulus, ductility, and thermal stability can be obtained; (3) polyurethanes having an improved fluidity and processability in molding can be obtained; (4) polyurethanes having an excellent color hue and gloss and not causing bleeding and roughness on the surface can be obtained; and (5) molding or preparation machines are not choked or plugged with burnt polymers, etc.
  • R 1 is an alkylene group having a carbon number ranging from 1 to 10, specifically an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group.
  • unsaturated compounds having the alkylene group R 1 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, etc.
  • R 2 is an alkylene group having a carbon number ranging from 1 to 10, specifically a trimethylene group, 2-methyltrimethylene group, 2,2-dimethyltrimethylene group, or tetramethylene group which depends upon the cyclic carbonate monomer to be employed.
  • air or oxygen is preferably employed in the preparation of the (meth)acrylic-modified (co)polymers in order to prevent radical polymerization of the starting hydroxyalkyl (meth) acrylate and the resulting (co)polymer.
  • nl, n2, or n1+n2 is preferably from 1 to 10, respectively, because a (meth)acrylic-modified (co)polymer having n1, n2 or n1+n2 more than 10 is not so much employed in specific applications.
  • the (meth)acrylic-modified (co)polymers of the present invention are characterized in that n1, n2, or n1+n2 is in highly good order in above-described general formulae (IV), (V), or (VI).
  • polymers are admixtures composed of (meth)acrylic-modified lactone polymers having different molecular weights.
  • the (meth)acrylic-modified (co)polymers of the present invention are monodispersed, and thereby there can be minutely controlled physical and chemical properties in products such as starting materials for coatings and modifiers for polymers, and further reactivity and workability in manufacturing the products are exceedingly fine.
  • a random copolymer can be prepared, and, when either one monomer is charged to carried out polymerization, and then another monomer is charged after the polymerization was completed, a block copolymer can be prepared.
  • the monodispersed (meth)acrylic-modified (co)polymers of the present invention are employed, for example, in fields of coatings as described in the Japanese Patent Kokoku No. 25322/1989 in which styrene, methylmethacrylate, and a (meth)-acrylic-modified lactone polymer are employed as resins for coatings, the following three advantages would be newly provided; (1) for example, in the case when a cured coating layer is formed by the above-described radical copolymer and polyvalent isocyanates, the coating layer is excellent in properties of the coating layer, for example, modulus, flexibility, weatherability, scratch resistance, low temperature resistance, and workability in coating, etc., because of an averaged reactivity of terminated hydroxyl groups in the (meth)acrylic-modified lactone polymer, resulting in forming a high crosslinked density and forming a coating layer having averaged cross-linked structures; (2) various properties such as radical polymerizability, storage stability, and crystallization temperatures, etc
  • 2,6-ditert-butyl-methylphenol (2.76 g, 12.5 millimol) was dissolved into 10 ml of dried hexane, and then trimethyl-aluminum (0.6 ml, 6.25 millimol) was added dropwise at 0° C. to obtain a suspension.
  • the suspension obtained was heated to 60° C. in order to dissolve it. After the suspension was completely dissolved, it was placed for 10 hours at room temperatures to obtain an aluminum-based Lewis acid substituted by two-fold by mol of 2,6-ditert-butyl-methylphenol (hereinafter, referred to as MeAlBMP) which is a white-colored crystalline.
  • MeAlBMP 2,6-ditert-butyl-methylphenol
  • the crystalline was washed twice with dried hexane, and dried in vacuo.
  • the crystalline was employed without any treatments or as a dichloromethane solution containing 0.3 millimol/ml after weighing.
  • 2,6-diphenylphenol (7.4 g, 30 millimol) was dissolved into 42.5 ml of dried toluene, and then 7.5 ml of 2.0 M toluene solution of trimethylaluminum was added dropwise at room temperatures to obtain an aluminum-based Lewis acid substituted by two-fold by mol of 2,6-diphenylphenol (hereinafter, referred to as MeAlDPP).
  • MeAlTCP an aluminum-based Lewis acid substituted by two-fold of 2,4,6-trichlorophenol
  • 2,6-ditert-butyl-4-methylphenol (4.4 g, 20 millimol) was dissolved into 30 ml of dried hexane, and then 20 ml of 0.5 M hexane solution of triisobutylaluminum was added dropwise at 0° C. to obtain an aluminum-based Lewis acid substituted by 2,6-ditert-butyl-4-methylphenol (hereinafter, referred to as iso-BuAlBmP).
  • Reactant was supplied to 300 ml of methanol to obtain a white-colored precipitation.
  • the white-colored precipitation was dried at reduced pressures to obtain 2.55 g of a carbonate polymer having number average molecular weight of 2,200 based on a standard Polystyrene and molecular weight distribution of 1.15 measured with a GPC.
  • FIG. 1 is an 1 H-NMR chart related to the carbonate polymer. It was confirmed that 20-fold by mol of neopentyl glycol carbonate is added to isopropyl alcohol as charged.
  • Example 2 No. 1 living polymerization of epsilon-caprolactone>
  • Example 2 The same equipment as described in Example 1 was charged with epsilon-caprolactone (2.2 ml, 20 millimol) by the same methods. A dried dichloromethane (1.6 ml) and isopropyl alcohol (0.077 ml, 1 millimol) were added, and further there was added ml of a dichloromethane solution containing 0.3 millimol/ml of MeAlBMP, followed by polymerizing to obtain 2.10 g of a caprolactone polymer having a number average molecular weight of 5,400 based on a standard Polystyrene and molecular weight distribution of 1.15 measured with a GPC.
  • FIG. 2 is an 1 H-NMR chart related to the caprolactone polymer. It was confirmed that 20-fold by tool of epsilon-caprolactone is added to isopropyl alcohol as charged.
  • Example 2 The same equipment as described in Example 1 was charged with neopentyl glycol carbonate (6.5 g, 50 millimol), followed by purging with nitrogen gas.
  • ⁇ -caprolactone 5.5 ml, 50 millimol was added, followed by proceeding with copolymerization while stirring for 1.5 hours at room temperatures to obtain a reaction mixture.
  • the reaction mixture was supplied to 300 ml of methanol to obtain a white-colored precipitation, followed by drying it at reduced pressures to obtain 11.6 g of a block copolymer.
  • FIG. 3 shows GPC chart related to the neopentyl glycol carbonate polymer which was obtained by sampling and the block copolymer produced. It was confirmed by the GPC chart that the molecular weight was increased by block copolymerization.
  • the number average molecular weight in the former neopentyl glycol carbonate polymer is 6,200 and the molecular weight distribution is 1.18
  • the number average molecular weight in the block copolymer is 13,400 and the molecular weight distribution is 1.20.
  • FIG. 4 is an 1 H-NMR chart related to the block copolymer, and shows that the molar ratio of isopropyl alcohol/neopentyl glycol carbonate/epsilon-caprolactone is 1.0/50.0/46.8.
  • Example 2 The same equipment as described in Example 1 was charged with epsilon-caprolactone (11.0 ml, 100 millimol), a dried dichloro-methane (3 ml), isopropyl alcohol (0.077 ml, 1 millimol), and 1 ml of a toluene solution containing 0.3 millimol/ml Of MeAlDPP prepared in Preparation Example 2, followed by stirring at room temperatures for 5 hours. ⁇ -caprolactone completely disappeared during stirring.
  • Example 2 The same operations as described in Example 1 were carried out to obtain 10.8 g of a lactone polymer having a number average molecular weight of 13,300 based on standard Polystyrene and the molecular weight distribution is 1.11 by a measurement with GPC.
  • a 4-necked flask equipped with a tube for introducing air, a thermostat, a condenser, and a stirrer was charged with 2-hydroxyethylmethacrylate (130 g, 1 mol), epsilon-caprolactone (456.6 g, 4 mol), and 3 ml of 0.3 M-toluene solution of MeAlDPP prepared in Preparation Example 2, followed by stirring at 60° C. for 5 hours while streaming a dried air to obtain a dope.
  • a GPC measurement was carried out related to the dope obtained, and the dope was diluted by toluene, and then the diluted dope was refined by separation with a silica-gel column and removal of solvent to obtain 582 g of a monodispersed methacrylic-modified epsilon-caprolactone tetramer.
  • Example 5 In order to make a comparison with Example 5, the same equipment, charging, and reaction conditions as described in Example 5 were applied, except that 3 ml of a toluene solution containing 0.3 M of monobutyltintris (2-ethylhexanate) was employed in place of the catalyst employed in Example 5 to prepare a monodispersed methacrylic-modified epsilon-caprolactone tetramer. It required 32 hours until the residual amount of epsilon-caprolactone attains to less than 1%. A GPC measurement was carried out related to the dope obtained.
  • 3 ml of a toluene solution containing 0.3 M of monobutyltintris (2-ethylhexanate) was employed in place of the catalyst employed in Example 5 to prepare a monodispersed methacrylic-modified epsilon-caprolactone tetramer. It required 32 hours until the residual amount of epsilon-caprolact
  • Example 5 The same equipment as described in Example 5 was charged with 2-hydroxyethylacrylate (116.1 g, 1 mol), propyleneglycol carbonate (204.1 g, 2 mol), and 5 ml of 0.3 M toluene solution of MeAlTCP obtained in Preparation Example 3, followed by stirring at 60° C. for 6 hours while streaming a dried air to obtain a dope.
  • a GPC measurement was carried out related to the dope obtained, and the dope was diluted by toluene, and then the diluted dope was refined by separation with a silica-gel column and removal of solvent to obtain 314 g of a monodispersed acrylic-modified carbonate dimer. Results of the GPC measurement are shown in Table 2.
  • Example 2 The same equipment as described in Example 1 was charged with ethyleneglycol (31 g, 0.5 mol ), epsilon-caprolactone (970.2 g, 8.5 mol), and MeAlBMP (7.21 g, 15 millimol) prepared in Prepa-ration Example 1, followed by stirring at 65° C. for 6 hours while streaming a dried air to obtain a diol. A GPC measurement was carried out related to the diol obtained, and then 500 ml of methanol was added, followed by stirring while refluxing of methanol. 999.4 g of a monodispersed polylactone diol was obtained by separation of the methanol layer.
  • Example 7 In order to make comparison with Example 7, the same equipment, charging, and reaction conditions as described in Example 7 were applied, except that tetrabutyltitanate (5.10 g, 15 millimol) was employed in place of the catalyst MeAlBMP (7.21 g, 15 millimol) employed in Example 7 to prepare a polylactone diol. It required 46 hours until the residual amount of epsilon-caprolactone attains to less than 1%. A GPC measurement was carried out related to the dope obtained.
  • Example 2 The same equipment as described in Example 1 was charged with trimethylol propane (67.1 g, 0.5 mol), delta-varelolactone (400.4 g, 4 mol), and MeAlBMP (4.81 g, 10 millimol) prepared in Preparation Example 1, followed by stirring at 65° C. for 4 hours while streaming a dried air to obtain a triol. A GPC measurement was carried out related to the triol obtained, and then 500 ml of methanol was added, followed by stirring while refluxing methanol. 459.7 g of a monodispersed polylactone triol was obtained by the separation of the methanol layer.
  • Example 5 The same equipment as described in Example 5 was charged with 2-hydroxyethylmethacrylate (260.3 g, 2 mol), neopentyl glycol carbonate (260.3 g, 2 mol), and 3 ml of 0.2 M hexane solution of iso-BuMeAlBMP obtained in Preparation Example 4, followed by stirring at 100° C. for 4 hours while introducing dried air to obtain a dope. A GPC measurement was carried out related to tile dope obtained. Results of the GPC measurement are shown in Table 2.
  • Example 2 The same equipment as described in Example 1 was charged with epsilon-caprolactone (5.5 ml, 50 millimol) and 4 ml of a dichloromethane solution containing 0.025 millimol/ml of methanol by the same methods as described in Example 1, and then there was added 2.5 ml of 0.3 M dichloromethane solution of MeAlDPP obtained in Preparation Example 2, followed by stirring at room temperatures for 42 hours to obtain a reaction mixture. The reaction mixture was supplied into 300 ml of methanol to obtain a white-colored precipitation, followed by drying it at reduced pressures to obtain a polymer. The number average molecular weight of the polymer was 62,600 based on a standard Polystyrene and molecular weight distribution measured with a GPC was 1.14.
  • FIG. 5 is a GPC chart related to the polymer.
  • Example 11 No. 2 preparation of a neopentyl glycol carbonate-epsilon-caprolactone block copolymer>
  • Example 2 The same equipment as described in Example 1 was charged with epsilon-caprolactone (5.5 ml, 50 millimol) and isopropyl alcohol (0.077 ml, 1 millimol) and dichloromethane (4 ml) with a syringe while streaming nitrogen gas, and further there was added 2.5 ml of 0.3 M dichloromethane solution of MeAlDPP prepared in Preparation Example 2, followed by stirring for 2.5 hours at room temperatures and sampling of a minor amount to confirm complete disappearance of epsilon-caprolactone.
  • epsilon-caprolactone 5.5 ml, 50 millimol
  • isopropyl alcohol 0.077 ml, 1 millimol
  • dichloromethane 4 ml
  • FIG. 6 shows a GPC chart related to the caprolactone polymer which was obtained by sampling and the block copolymer produced. It was confirmed by the GPC chart that the molecular weight increased by the block copolymerization. While the number average molecular weight in the former epsilon-caprolactone polymer is 6,400 and the molecular weight distribution is 1.19, number average molecular weight in the block copolymer is 20,000 and the molecular weight distribution is 1.17.
  • Example 12 No. 1 preparation of a monodispersed neopentyl glycol carbonate-epsilon-caprolactone random copolymer>
  • Example 2 The same equipment as described in Example 1 was charged with ethyleneglycol (18.6 g, 0.3 millimol), neopentyl glycol carbonate (195.2 g, 1.5 mol), epsilon-caprolactone (399.5 g, 3.5 mol). Successively, 10 ml of 0.2 M hexane solution of iso-BuAlBMP prepared in Preparation Example 4, followed by stirring at 150° C. for 2 hours while streaming a dried nitrogen gas to obtain a copolymer. A GPC measurement was carried out related to the copolymer obtained. The results of GPC measurement related to the copolymer obtained are shown in Table 3.
  • Example 13 No. 2 preparation of a monodispersed neopentyl glycol carbonate-epsilon-caprolactone random copolymer>
  • Example 2 The same equipment as described in Example 1 was charged with ethyleneglycol (18.6 g, 0.3 millimol), neopentyl glycol carbonate (65.1 g, 0.5 mol), epsilon-caprolactone (513.6 g, 4.5 mol) . Successively, 10 ml of 0. 5 M hexane solution of isoBuAlBMP prepared in Preparation Example 4, followed by stirring at 150° C. for 2 hours while streaming dried nitrogen gas to obtain a copolymer. A GPC measurement was carried out related to the copolymer obtained. Results of the GPC measurement related to the copolymer obtained are shown in Table 3.
  • Respective crystallinity related to the (co)polymers obtained in Examples 7, 12, 13, and Comparative Example 2 was evaluated by the presence or absence of crystallinity after being placed at 0° C., 20° C., and 40° C., respectively, for 1 week.
  • component ratio (%) is represented by the area percent (%) of a peak by dope before refining minus a peak by toluene.
  • component ratio (%) is represented by the area percent (%) of a peak by dope before refining minus a peak by toluene.
  • NAMW represents the number average molecular weight
  • MWD represents the molecular weight distribution
  • WCS means "white-colored solid" and TL means "transparent liquid”.
  • Table 4 clearly shows that when the ratio of neopentyl glycol carbonate with respect to epsilon-caprolactone is larger, crystallinity in the (co)polymers is more reduced, and crysta-llinity in the (co)polymers does not so much depend upon catalysts.
  • a polyol for example, a polylactonediol or carbonatediol, etc.
  • a polyurethane which is a starting material for polyurethanes is preferably employed in the state of a liquid or a solid having a low melting point from the viewpoint of workability during the preparation of polyurethanes.

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Cited By (5)

* Cited by examiner, † Cited by third party
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US6083524A (en) 1996-09-23 2000-07-04 Focal, Inc. Polymerizable biodegradable polymers including carbonate or dioxanone linkages
US20090036645A1 (en) * 2007-07-30 2009-02-05 Stopek Joshua B Carbonate copolymers
US20120108786A1 (en) * 2009-03-31 2012-05-03 Arkema France Organic system for the ring-opening polymerization of cyclic carbonates in order to obtain (bio)-polycarbonates
WO2013030324A1 (en) * 2011-09-02 2013-03-07 Total Research & Technology Feluy Catalyst systems based on phenolate complexes for immortal ring-opening polymerisation of cyclic esters and carbonates
CN117343217A (zh) * 2022-06-29 2024-01-05 中国科学院青岛生物能源与过程研究所 一种改性铝及其制备、高机械性能丙烯酸酯热塑性弹性体及其制备方法和应用

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EP0783009B1 (de) 1995-12-01 2005-01-26 Hokushin Corporation Verfahren zur Herstellung von walzbaren Polyurethanen und Polyurethanelastomeren
EP0776921A3 (de) * 1995-12-01 1997-08-13 Hokushin Corp Verfahren zur Herstellung von amorphen Polymerketten in Elastomeren
US6008312A (en) * 1995-12-01 1999-12-28 Hokushin Corp Method for producing millable polyurethanes and polyurethane elastomers
US6191250B1 (en) * 1997-10-15 2001-02-20 Daicel Chemical Industries, Ltd. Processes for the preparation of a monodisperse polymers, processes for the continuous polymerization of cyclic monomers, and polymers prepared thereby
JP4560374B2 (ja) * 2004-10-28 2010-10-13 旭化成ケミカルズ株式会社 水酸基末端を有するポリカーボネート／ポリエーテルブロック共重合体
JP4560373B2 (ja) * 2004-10-28 2010-10-13 旭化成ケミカルズ株式会社 末端に水酸基を有するポリカーボネート／ポリエーテルブロック共重合体
JP4686754B2 (ja) * 2005-02-07 2011-05-25 独立行政法人産業技術総合研究所 含アルミニウムデンドリマー、その製造方法及び該デンドリマーからなる含アルミニウムルイス酸触媒
EP2196486A1 (de) * 2008-12-12 2010-06-16 Total Petrochemicals Research Feluy Verfahren zur Herstellung von Di- und Multiblock-Copolymeren
US8608988B2 (en) * 2010-11-23 2013-12-17 Transitions Optical, Inc. Curable photochromic compositions and optical articles prepared therefrom
JP7572184B2 (ja) * 2019-09-20 2024-10-23 保土谷化学工業株式会社 ラクトン重合体の製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095098A (en) * 1989-09-29 1992-03-10 E. I. Du Pont De Nemours And Company Yttrium and rare earth compounds catalyzed lactone polymerization

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4699974A (en) 1986-08-07 1987-10-13 General Electric Company Method of preparing copolyester carbonate from cyclic aromatic polycarbonate oligomer and lactone

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095098A (en) * 1989-09-29 1992-03-10 E. I. Du Pont De Nemours And Company Yttrium and rare earth compounds catalyzed lactone polymerization

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US6083524A (en) 1996-09-23 2000-07-04 Focal, Inc. Polymerizable biodegradable polymers including carbonate or dioxanone linkages
US6177095B1 (en) 1996-09-23 2001-01-23 Focal, Inc Polymerizable biodegradable polymers including carbonate or dioxanone linkages
USRE39713E1 (en) 1996-09-23 2007-07-03 Genzyme Corporation Polymerizable biodegradable polymers including carbonate or dioxanone linkages
US20090036645A1 (en) * 2007-07-30 2009-02-05 Stopek Joshua B Carbonate copolymers
US7666973B2 (en) 2007-07-30 2010-02-23 Tyco Healthcare Group Lp Carbonate copolymers
US20120108786A1 (en) * 2009-03-31 2012-05-03 Arkema France Organic system for the ring-opening polymerization of cyclic carbonates in order to obtain (bio)-polycarbonates
WO2013030324A1 (en) * 2011-09-02 2013-03-07 Total Research & Technology Feluy Catalyst systems based on phenolate complexes for immortal ring-opening polymerisation of cyclic esters and carbonates
CN103906787A (zh) * 2011-09-02 2014-07-02 道达尔研究技术弗吕公司 用于环状酯和碳酸酯的永活性开环聚合的基于酚根络合物的催化剂体系
US9512267B2 (en) 2011-09-02 2016-12-06 Total Research & Technology Feluy Catalyst systems based on phenolate complexes for immortal ring-opening polymerization of cyclic esters and carbohydrates
CN117343217A (zh) * 2022-06-29 2024-01-05 中国科学院青岛生物能源与过程研究所 一种改性铝及其制备、高机械性能丙烯酸酯热塑性弹性体及其制备方法和应用

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